CN103012194B - Nitrine ester compound and synthesis method thereof - Google Patents

Nitrine ester compound and synthesis method thereof Download PDF

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CN103012194B
CN103012194B CN201210464144.3A CN201210464144A CN103012194B CN 103012194 B CN103012194 B CN 103012194B CN 201210464144 A CN201210464144 A CN 201210464144A CN 103012194 B CN103012194 B CN 103012194B
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acetic acid
nitrine
mol ratio
dinitrobutane
dichloro acetic
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CN103012194A (en
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周新利
王娟
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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Abstract

The invention provides a nitrine ester compound and a synthesis method thereof, wherein 1,4-biazidocarbethoxy-2,3-biazidocarbethoxymethyl-2,3-binitrobutane is synthesized by taking 2,3-bihydroxymethyl-2,3-binitro-1,4-butanediol as a raw material to be subjected to two steps of reactions of esterification and nitridation; and 1HNMR (1h Nuclear Magnetic Resonance) and IR (Infrared Radiation) are used for characterizing structures of a target product and an intermediate body. Two solvents including toluene and dimethylbenzene are used for carrying out esterification reaction; the dimethylbenzene is a better solvent of the reaction; catalysts including concentrated sulfuric acid, phosphoric acid and p-toluenesulfonic acid are compared to obtain that the p-toluenesulfonic acid is a better catalyst of the esterification reaction; and the nitridation reaction is discussed to determine that tetrabutylammonium bromide is a better phase transfer catalyst of the reaction.

Description

A kind of nitrine ester compound and synthetic method thereof
Technical field
The present invention relates to a kind of nitrine ester compound and synthetic method thereof, particularly Isosorbide-5-Nitrae-bis-nitrine acetoxyl-2,3-bis-nitrine acetic acid methyl-2,3-dinitrobutane and synthetic, belongs to organic chemistry filed.
Background technology
Organic azide is the energetic material of a class excellence, is widely used in containing all many-sides such as energy tamanori, energetic plasticiser, oxygenants, and be to improve the energy level of energetic material and the important channel of technical feature.
Conventional energetic plasticiser has the types such as nitrate esters energetic plasticiser, geminal dinitro class energetic plasticiser, nitrine class energetic plasticiser, nitre oxygen ethyl nitramine class energetic plasticiser at present.Compound Isosorbide-5-Nitrae-bis-nitrine acetoxyl-2 of synthesized of the present invention, 3-bis-nitrine acetic acid methyl-2,3-dinitrobutane is simultaneously containing two nitros and two kinds of nitrine ester compounds containing energy group of four azido-s.
At present about Isosorbide-5-Nitrae-bis-nitrine acetoxyl-2,3-bis-nitrine acetic acid methyl-2, the synthetic report that has no of 3-dinitrobutane.And similar compound synthetic generally to adopt polyvalent alcohol and Mono Chloro Acetic Acid be raw material, toluene is solvent, sour for catalyzer refluxes, and obtains precursor chloro ester, then in dimethyl sulfoxide (DMSO) (DMSO) with sodiumazide (NaN 3) reaction, make nitrine ester plasticizer.
This softening agent shortcoming is that nitrogen content is low, little to the contribution of propelling agent maximum system energy, raw material 2 of the present invention, 3-dihydroxymethyl-2,3-dinitrobenzene-1,4-butyleneglycol, is the tetravalent alcohol that contains two nitros, prepared by it 1,4-bis-nitrine acetoxyl-2,3-bis-nitrine acetic acid methyl-2,3-dinitrobutane, is the nitrine ester plasticizer containing two nitros and four azido-s, symmetrical configuration, molecular stability is good, changes the physicals that carbon bond length can keep triazo-compound simultaneously, and being expected to has certain contribution to the energy of propelling agent system.
Summary of the invention
The object of the present invention is to provide a kind of new nitrine ester compound and synthetic method thereof.
The technical scheme that realizes the object of the invention is: a kind of nitrine ester compound, has following structure:
The synthetic route of the nitrine ester compound of said structure is as follows:
A kind of nitrine ester compound is prepared by following steps:
In step 1, esterification 2,3-dihydroxymethyl-2,3-dinitrobenzene-BDO and chloroacetic mol ratio are 1:4～6, add catalyzer, reflux, fraction water device water-dividing;
Step 2, Isosorbide-5-Nitrae-dichloro acetic acid base-2,3-dichloro acetic acid methyl-2, the mol ratio of 3-dinitrobutane and sodiumazide is 1:4～6, and dimethyl sulphoxide aqueous solution is solvent, and Tetrabutyl amonium bromide is phase-transfer catalyst, stirring at room temperature, is slowly warming up to 30～100 DEG C of reactions.
The solvent of the esterification described in step 1 can adopt toluene or dimethylbenzene, and described catalyzer can be the vitriol oil or tosic acid etc., described catalyzer and 2, and 3-dihydroxymethyl-2, the mol ratio of 3-dinitrobenzene-BDO is 0.025:1.
The mass concentration of the dimethyl sulphoxide aqueous solution described in step 2 is 95%, described Tetrabutyl amonium bromide and Isosorbide-5-Nitrae-dichloro acetic acid base-2, and 3-dichloro acetic acid methyl-2,3-dinitrobutane mol ratio is 3:100, the described stirring at room temperature time is 2h.
Beneficial effect
1. Isosorbide-5-Nitrae-bis-nitrine acetoxyl-2,3-bis-nitrine acetic acid methyl-2,3-dinitrobutane there is not yet bibliographical information.
2. Isosorbide-5-Nitrae-bis-nitrine acetoxyl-2,3-bis-nitrine acetic acid methyl-2,3-dinitrobutane, is two kinds of nitrine ester classes containing energy functional group containing two nitros and four azido-s, being expected to has certain contribution to the energy of propelling agent system.
The tosic acid of 3 cheapnesss is in esterification, and consumption is little, active high, is difficult for causing side reaction, therefore, has certain economy and the feature of environmental protection.
4. Tetrabutyl amonium bromide is phase-transfer catalyst, has improved the speed of azido reaction.
5. reaction conditions of the present invention is gentle and be easy to control, low for equipment requirements.
Brief description of the drawings
Fig. 1 is Isosorbide-5-Nitrae-dichloro acetic acid base-2,3-dichloro acetic acid methyl-2,3-dinitrobutane 1h NMR.
Fig. 2 is Isosorbide-5-Nitrae-dichloro acetic acid base-2,3-dichloro acetic acid methyl-2, the IR of 3-dinitrobutane.
Fig. 3 is Isosorbide-5-Nitrae-bis-nitrine acetoxyl-2,3-bis-nitrine acetic acid methyl-2,3-dinitrobutane 1h NMR.
Fig. 4 is Isosorbide-5-Nitrae-bis-nitrine acetoxyl-2,3-bis-nitrine acetic acid methyl-2, the IR of 3-dinitrobutane.
Embodiment
Embodiment 1
Intermediate product Isosorbide-5-Nitrae-dichloro acetic acid base-2,3-dichloro acetic acid methyl-2, the preparation of 3-dinitrobutane
2,3-dihydroxymethyl-2,3-dinitrobenzene-1,4-butyleneglycol and chloroacetic mol ratio are 1:6, dimethylbenzene 50mL, tosic acid and 2,3-dihydroxymethyl-2,3-dinitrobenzene-1,4-butyleneglycol mol ratio is 0.025:1, refluxes, and fraction water device water-dividing, when the amount of the water separating reaches the theoretical amount generating, stopped reaction.Cooling, underpressure distillation, except removal xylene, product is dissolved in CH 2cl 2in, with the saturated NaHCO of 100mL (2 × 50mL) 3solution washing is extremely neutral, then uses NaCl solution washing three times, anhydrous magnesium sulfate drying, concentrating under reduced pressure, crude product sherwood oil: the eluent that acetone is 1:1, column chromatography for separation.Yield is 83.6%.
Fig. 1 from brief description of the drawings can find out, δ 4.21 is-CH 2the chemical shift of H on Cl; δ 5.74 is-CH 2the chemical shift of H on OOC.As can be seen from Figure 2,2959cm -1for C-H stretching vibration peak; 1747cm -1for C=O stretching vibration peak; 791 cm -1for C-Cl stretching vibration peak
Embodiment 2
Intermediate product Isosorbide-5-Nitrae-dichloro acetic acid base-2,3-dichloro acetic acid methyl-2, the preparation of 3-dinitrobutane
2,3-dihydroxymethyl-2,3-dinitrobenzene-1,4-butyleneglycol and chloroacetic mol ratio are 1:5, dimethylbenzene 50mL, tosic acid and 2,3-dihydroxymethyl-2,3-dinitrobenzene-1,4-butyleneglycol mol ratio is 0.025:1, refluxes, and fraction water device water-dividing, when the amount of the water separating reaches the theoretical amount generating, stopped reaction.Cooling, underpressure distillation, except removal xylene, product is dissolved in CH 2cl 2in, with the saturated NaHCO of 100mL (2 × 50mL) 3solution washing is extremely neutral, then uses NaCl solution washing three times, anhydrous magnesium sulfate drying, concentrating under reduced pressure, crude product sherwood oil: the eluent that acetone is 1:1, column chromatography for separation.Yield is 77.9%.
Embodiment 3
Intermediate product Isosorbide-5-Nitrae-dichloro acetic acid base-2,3-dichloro acetic acid methyl-2, the preparation of 3-dinitrobutane
2,3-dihydroxymethyl-2,3-dinitrobenzene-1,4-butyleneglycol and chloroacetic mol ratio are 1:4, dimethylbenzene 50mL, tosic acid and 2,3-dihydroxymethyl-2,3-dinitrobenzene-1,4-butyleneglycol mol ratio is 0.025:1, refluxes, and fraction water device water-dividing, when the amount of the water separating reaches the theoretical amount generating, stopped reaction.Cooling, underpressure distillation, except removal xylene, product is dissolved in CH 2cl 2in, with the saturated NaHCO of 100mL (2 × 50mL) 3solution washing is extremely neutral, then uses NaCl solution washing three times, anhydrous magnesium sulfate drying, concentrating under reduced pressure, crude product sherwood oil: the eluent that acetone is 1:1, column chromatography for separation.Yield is 71.8%.
Embodiment 4
Intermediate product Isosorbide-5-Nitrae-dichloro acetic acid base-2,3-dichloro acetic acid methyl-2, the preparation of 3-dinitrobutane
2,3-dihydroxymethyl-2,3-dinitrobenzene-1,4-butyleneglycol and chloroacetic mol ratio are 1:6, toluene 50mL, tosic acid and 2,3-dihydroxymethyl-2,3-dinitrobenzene-1,4-butyleneglycol mol ratio is 0.025:1, refluxes, and fraction water device water-dividing, when the amount of the water separating reaches the theoretical amount generating, stopped reaction.Cooling, underpressure distillation, removes toluene, and product is dissolved in CH 2cl 2in, with the saturated NaHCO of 100mL (2 × 50mL) 3solution washing is extremely neutral, then uses NaCl solution washing three times, anhydrous magnesium sulfate drying, concentrating under reduced pressure, crude product sherwood oil: the eluent that acetone is 1:1, column chromatography for separation.Yield is 74.9%.
Embodiment 5
Intermediate product Isosorbide-5-Nitrae-dichloro acetic acid base-2,3-dichloro acetic acid methyl-2, the preparation of 3-dinitrobutane
2,3-dihydroxymethyl-2,3-dinitrobenzene-1,4-butyleneglycol and chloroacetic mol ratio are 1:6, dimethylbenzene 50mL, the vitriol oil and 2,3-dihydroxymethyl-2,3-dinitrobenzene-1,4-butyleneglycol mol ratio is 0.025:1, refluxes, and fraction water device water-dividing, when the amount of the water separating reaches the theoretical amount generating, stopped reaction.Cooling, underpressure distillation, except removal xylene, product is dissolved in CH 2cl 2in, with the saturated NaHCO of 100mL (2 × 50mL) 3solution washing is extremely neutral, then uses NaCl solution washing three times, anhydrous magnesium sulfate drying, concentrating under reduced pressure, crude product sherwood oil: the eluent that acetone is 1:1, column chromatography for separation.Yield is 75.2%.
Embodiment 6
Nitrine ester Isosorbide-5-Nitrae-bis-nitrine acetoxyl-2,3-bis-nitrine acetic acid methyl-2, the preparation of 3-dinitrobutane
Isosorbide-5-Nitrae-dichloro acetic acid base-2 of embodiment 1 gained, 3-dichloro acetic acid methyl-2, the mol ratio of 3-dinitrobutane and sodiumazide is 1:6,95% DMSO aqueous solution 30mL, Tetrabutyl amonium bromide and 1,4-dichloro acetic acid base-2,3-dichloro acetic acid methyl-2,3-dinitrobutane mol ratio is 3:100, stirring at room temperature 2h, is slowly warming up to 50 DEG C, and TLC follows the tracks of reaction, reaction times, while being 15h, stopped reaction, was cooled to room temperature, pour in trash ice, stir CH 2cl 2extraction, CH 2cl 2use mutually salt water washing repeatedly, then wash with water, anhydrous magnesium sulfate drying, concentrated, yield is 82.3%.
Fig. 3 from brief description of the drawings can find out, δ 3.67 is-CH 2n 3on the chemical shift of H; δ 5.80 is-CH 2the chemical shift of H on OOC.As can be seen from Figure 4,2924cm -1for C-H stretching vibration peak; 2104 cm -1for-N 3stretching vibration peak; 1748cm -1for C=O stretching vibration peak.
Embodiment 7
Nitrine ester Isosorbide-5-Nitrae-bis-nitrine acetoxyl-2,3-bis-nitrine acetic acid methyl-2, the preparation of 3-dinitrobutane
Isosorbide-5-Nitrae-dichloro acetic acid base-2 of embodiment 1 gained, 3-dichloro acetic acid methyl-2, the mol ratio of 3-dinitrobutane and sodiumazide is 1:5,95% DMSO aqueous solution 30mL, Tetrabutyl amonium bromide and 1,4-dichloro acetic acid base-2,3-dichloro acetic acid methyl-2,3-dinitrobutane mol ratio is 3:100, stirring at room temperature 2h, is slowly warming up to 50 DEG C, and TLC follows the tracks of reaction, stopped reaction, is cooled to room temperature, pours in trash ice, stir CH 2cl 2extraction, CH 2cl 2use mutually salt water washing repeatedly, then wash with water, anhydrous magnesium sulfate drying, concentrated, yield is 78.4%.
Embodiment 8
Nitrine ester Isosorbide-5-Nitrae-bis-nitrine acetoxyl-2,3-bis-nitrine acetic acid methyl-2, the preparation of 3-dinitrobutane
Isosorbide-5-Nitrae-dichloro acetic acid base-2 of embodiment 1 gained, 3-dichloro acetic acid methyl-2, the mol ratio of 3-dinitrobutane and sodiumazide is 1:4,95% DMSO aqueous solution 30mL, Tetrabutyl amonium bromide and 1,4-dichloro acetic acid base-2,3-dichloro acetic acid methyl-2,3-dinitrobutane mol ratio is 3:100, stirring at room temperature 2h, is slowly warming up to 50 DEG C, and TLC follows the tracks of reaction, stopped reaction, is cooled to room temperature, pours in trash ice, stir CH 2cl 2extraction, CH 2cl 2use mutually salt water washing repeatedly, then wash with water, anhydrous magnesium sulfate drying, concentrated, yield is 70.3%.
Embodiment 9
Nitrine ester Isosorbide-5-Nitrae-bis-nitrine acetoxyl-2,3-bis-nitrine acetic acid methyl-2, the preparation of 3-dinitrobutane
Isosorbide-5-Nitrae-dichloro acetic acid base-2 of embodiment 1 gained, 3-dichloro acetic acid methyl-2, the mol ratio of 3-dinitrobutane and sodiumazide is 1:6,95% DMSO aqueous solution 30mL, Tetrabutyl amonium bromide and 1,4-dichloro acetic acid base-2,3-dichloro acetic acid methyl-2,3-dinitrobutane mol ratio is 3:100, stirring at room temperature 2h, is slowly warming up to 30 DEG C, and TLC follows the tracks of reaction, stopped reaction, is cooled to room temperature, pours in trash ice, stir CH 2cl 2extraction, CH 2cl 2use mutually salt water washing repeatedly, then wash with water, anhydrous magnesium sulfate drying, concentrated, yield is 77.0%.
Embodiment 10
Nitrine ester Isosorbide-5-Nitrae-bis-nitrine acetoxyl-2,3-bis-nitrine acetic acid methyl-2, the preparation of 3-dinitrobutane
Isosorbide-5-Nitrae-dichloro acetic acid base-2 of embodiment 1 gained, 3-dichloro acetic acid methyl-2, the mol ratio of 3-dinitrobutane and sodiumazide is 1:6,95% DMSO aqueous solution 30mL, Tetrabutyl amonium bromide and 1,4-dichloro acetic acid base-2,3-dichloro acetic acid methyl-2,3-dinitrobutane mol ratio is 3:100, stirring at room temperature 2h, is slowly warming up to 100 DEG C, and TLC follows the tracks of reaction, stopped reaction, is cooled to room temperature, pours in trash ice, stir CH 2cl 2extraction, CH 2cl 2use mutually salt water washing repeatedly, then wash with water, anhydrous magnesium sulfate drying, concentrated, yield is 79.8%.
Comparative example 1
Nitrine ester Isosorbide-5-Nitrae-bis-nitrine acetoxyl-2,3-bis-nitrine acetic acid methyl-2, the preparation of 3-dinitrobutane
Isosorbide-5-Nitrae-dichloro acetic acid base-2 of embodiment 1 gained, 3-dichloro acetic acid methyl-2, the mol ratio of 3-dinitrobutane and sodiumazide is 1:6, and 95% DMSO aqueous solution 30mL, does not add Tetrabutyl amonium bromide, stirring at room temperature 2h, is slowly warming up to 50 DEG C, and TLC follows the tracks of reaction, reaction times is 30h, stopped reaction, is cooled to room temperature, pours in trash ice, stir CH 2cl 2extraction, CH 2cl 2use mutually salt water washing repeatedly, then wash with water, anhydrous magnesium sulfate drying, concentrated, yield is 79.2%.
Comparative example 2
Nitrine ester Isosorbide-5-Nitrae-bis-nitrine acetoxyl-2,3-bis-nitrine acetic acid methyl-2, the preparation of 3-dinitrobutane
Isosorbide-5-Nitrae-dichloro acetic acid base-2 of embodiment 1 gained, 3-dichloro acetic acid methyl-2, the mol ratio of 3-dinitrobutane and sodiumazide is 1:6, and 95% DMSO aqueous solution 30mL, does not add Tetrabutyl amonium bromide, stirring at room temperature 2h, slowly be warming up to 80 DEG C, the reaction times is 15h, stopped reaction, be cooled to room temperature, pour in trash ice, stir CH 2cl 2extraction, CH 2cl 2use mutually salt water washing repeatedly, then wash with water, anhydrous magnesium sulfate drying, concentrated, yield is 81.6%.
From comparative example 1 and 2, Tetrabutyl amonium bromide has improved the speed of azido reaction as phase-transfer catalyst.

Claims (4)

1. a nitrine ester compound, is characterized in that described compound has following structure:
。
2. a synthetic method for nitrine ester compound, is characterized in that said method comprising the steps of:
In step a, esterification 2,3-dihydroxymethyl-2,3-dinitrobenzene-BDO and chloroacetic mol ratio are 1:4～6, add catalyzer, reflux, fraction water device water-dividing;
Step b, Isosorbide-5-Nitrae-dichloro acetic acid base-2,3-dichloro acetic acid methyl-2, the mol ratio of 3-dinitrobutane and sodiumazide is 1:4～6, and dimethyl sulphoxide aqueous solution is solvent, and Tetrabutyl amonium bromide is phase-transfer catalyst, stirring at room temperature, is slowly warming up to 30～100 DEG C of reactions.
3. the synthetic method of nitrine ester compound according to claim 2, the solvent that it is characterized in that the esterification described in step a adopts toluene or dimethylbenzene, described catalyzer is the vitriol oil or tosic acid, described catalyzer and 2,3-dihydroxymethyl-2, the mol ratio of 3-dinitrobenzene-BDO is 0.025:1.
4. the synthetic method of nitrine ester compound according to claim 2, the mass concentration that it is characterized in that the dimethyl sulphoxide aqueous solution described in step b is 95%, described Tetrabutyl amonium bromide and 1,4-dichloro acetic acid base-2,3-dichloro acetic acid methyl-2,3-dinitrobutane mol ratio is 3:100, and the described stirring at room temperature time is 2h.
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CN103172086A (en) * 2013-04-03 2013-06-26 南京理工大学 Phase stabilized ammonium nitrate additive and preparation method of phase stabilized ammonium nitrate
CN103641723A (en) * 2013-12-13 2014-03-19 南京理工大学 2,3-Dihydroxymethyl-2,3-dinitro-1,4-butanediol tetraacetate and synthetic method thereof
CN103724208A (en) * 2013-12-13 2014-04-16 南京理工大学 2,3-dihydromethyl-2,3-binitro-1,4-butanediol tetrapropionate and synthesis method thereof
CN103880704A (en) * 2014-03-21 2014-06-25 南京理工大学 Azide ester compound, synthetic method and application of compound
CN105439897A (en) * 2015-11-18 2016-03-30 西南科技大学 Synthetic method of 2, 6-dinitro-p-diazido-methylbenzene

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US6998485B1 (en) * 2002-12-19 2006-02-14 The United States Of America As Represented By The Secretary Of The Army Polyazido compounds
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